Preparation of metal‐phosphorus hybridized nanomaterials and the action of metal centers on the flame retardancy of epoxy resin

The action of metals on the flame retardancy of thermoplastic has aroused much interest in recent years. However, their action on thermosets is still not clear. In this work, metal‐phosphorus hybridized nanomaterials with different metal centers were prepared via hydrothermal reaction between metal hydroxide/salts with phosphinic/phosphonic acids. The loading of these hybrids in epoxy (EP) resins resulted in great change on fire resistance. Thermogravimetric analysis, solid and gas phase analysis results indicated that the flame retardant action of the hybrids perhaps didn't take place following the conventional models in condensed and gas phase. It was found that the flame retardancy was greatly correlated with the action of metal centers with EP resin, which resulted in the formation of metal‐oxygen bonds and the delayed release of flammable compounds from EP resin. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45445.     

Study on flame retardancy of APP/PEPA/MoO3 synergism in vinyl ester resins

A range of flame retardant vinyl ester resins (VERs) samples have been produced containing different contents of PEPA (1-oxo-4-hydroxymethyl-2,6,7-trioxa-l-phosphabicyclo[2.2.2]octane), APP (ammonium polyphosphate), and MoO₃ (molybdenum trioxide). By investigating the flame retardancy of VER samples such as limiting oxygen index and UL-94, the synergistic flame retardance of APP, PEPA, and MoO3 has been revealed. The cone calorimeter is an instrument that measures the combustion data of samples. In the VER composites on fire, the synergistic smoke suppression effect of the APP, PEPA, and MoO₃ was detected. The gas and condensed phase of VER composites with APP, PEPA, and MoO₃ were tested by the thermogravimetric analysis (TGA)–Fourier transform infrared spectroscopy (FTIR) and FTIR. The char residues of samples have been studied at length by scanning electron microscopy and FTIR. The results show that the presence of MoO3 can promote the formation of P O and PO structures.     

Preparation of ferric phosphonate/phosphinate and their special action on flame retardancy of epoxy resin

Fe‐ and P‐based compounds have demonstrated promising performance in enhancing flame retardancy of epoxy resins. In this context, this work focuses on the preparation of new Fe/P hybridized nanomaterials and their effect on flame retardancy of epoxy resins. The Fe/P hybrids were facilely prepared via forming ferric phosphinates and phosphonates using hydrothermal reaction. Attractively, ferric phosphinates and phosphonates exhibit the morphology of 1D nanorod and 2D nanosheet, respectively. When incorporating these two fillers in epoxy resin, the limiting oxygen index values of composites were enhanced to above 28 and the composites exhibited self‐extinguishing behavior, thus indicating greatly improved fire resistance. Further investigation revealed that the flame retarding behavior, in particular for ferric phosphonate nanosheets, took place mainly in gas phases via delaying the release of flammable gas. Attractively, it was found that the Fe/P hybrids took part into the pyrolysis reaction of epoxy resins through forming Fe? O and P? O bonds. This finding may provide a new insight to design a series of high performance flame retardants for epoxy resins. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46206.     

Novel strategy for molybdenum disulfide nanosheets grown on titanate nanotubes for enhancing the flame retardancy and smoke suppression of epoxy resin

A novel hybrid consisting of a molybdenum disulfide (MoS₂) coating on a titanium dioxide nanotube (TNT) surface (MoS₂–TNT) was synthesized by a hydrothermal method. The MoS₂, TNTs, and MoS₂–TNT hybrid were incorporated into epoxy resin (EP) to study their effects on its thermal performance and flame retardancy. Thermogravimetric analysis results show that the char yield at 700 °C of EP–MoS₂–TNTs was obviously increased compared with that of the EP–MoS₂ or EP–TNTs; this indicated that MoS₂–TNTs had a good carbonization effect. The limiting oxygen index, cone calorimetry, and smoke density tests showed that MoS₂–TNTs effectively improved the flame retardancy and smoke suppression of EP. This was attributed to the physical barrier effect of MoS₂ and the adsorption of TNTs. Moreover, the flame retardancy and smoke suppression of the EP–MoS₂–TNTs were better than those of the EP–MoS₂ or EP–TNTs alone with the same amount of addition; this indicated that there was a synergistic effect between MoS₂ and TNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46064.     

Preparation of alginate flame retardant containing P and Si and its flame retardancy in epoxy resin

In the present paper, a novel biomass flame retardant based on alginic acid was synthesized through chemical combination with a reactive P–Si compound. Compared with alginates, the modified alginate showed obviously increased thermal stability and water resisting property, as well as better compatibility with epoxy resin, which can satisfy the requirements of a flame‐retardant additive in the polymer. The flame‐retardant properties were evaluated by vertical burning tests, limiting oxygen index, and microscale combustion calorimetry. Due to the self‐charring capacity of alginate combined with the charring catalyst from P and the charring reinforcer from Si, the modified alginate exhibited much better flame retardancy, taking advantage of the formation of a more continuous, denser, and strengthened char layer than either individual alginate or P–Si flame retardant. The corresponding flame‐retardant mechanisms were investigated and discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45552.     

Improving flame retardancy and melt processability of polyethersulfone using low molecular weight additives

The effect of a calcium stearate (CaSt₂) additive on the melt processability and flame retardancy of polyethersulfone (PES) was studied. Measurements of the viscosity of PES and its composites showed a marked decrease in viscosity with increase in the fraction of CaSt₂ additive. About 40% reduction in viscosity of PES was achieved with addition of 5 wt % CaSt₂. By decreasing the viscosity, the CaSt₂ additive enabled the melt extrusion of PES at lower temperatures up to 90 °C below that of conventional melt processing. The flammability was also investigated using a Pyrolysis Combustion Flow Calorimeter (PCFC). The CaSt₂ additive resulted in tremendous improvement in the flame retardancy of PES as evident in the reduction of the heat release capacity (HRC) of the composites by up to 37%. Moreover, the peak of heat release rate (pHRR) of PES in the composites was up to 84% lower than in the neat polymer. The remarkable improvement in flame retardancy of PES was demonstrated to be related to the rapid charring of the composites and the in situ formation of calcium carbonate/calcium oxide upon decomposition of CaSt₂. The CaSt₂ additive was also found to enhance the flame retardancy of thermoplastics including polyamide‐6 and polypropylene (PP). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43525.     

Synthesis and characterization of dicyclic silicon-/phosphorus-grafted alumina and its application in improving flame retardancy of epoxy resin

A new phosphorous/silicon/aluminum hybrid flame retardant (SAlu) was prepared by a surface grafting modification of alumina with a polymer (SDPS). The polymer was prepared by a condensation reaction between 3,9-dichloro-2,4,8,10-tetrahydroxy-3,9-diphosphate heterocyclic-3,9-dioxide [5.5] undecane (SPDPC) and diphenyldisiloxol. The structure of the SAlu was further characterized by Fourier transform infrared spectroscopy, X-ray diffraction, UV–Vis absorption, and particle size analysis. Thermogravimetric analysis showed that SPDS was grafted over 40% of the alumina surface. When introduced into epoxy resin, SAlu effectively improved the thermal stability and carbonization rate of the epoxy composites at high temperature. Carbonization studies showed that SAlu promoted formation of a ceramic-carbon coking structure with a porous morphology of aggregates, which isolate combustible materials, heat, and oxygen. These features improved the flame retardant performance of the composite. The solidified materials were evenly dispersed in the network structure to improve the elastic deformation ability and glass transition temperature of the solidified resin.     

Synergistic effect of aluminum hydroxide and expandable graphite on the flame retardancy of polyisocyanurate–polyurethane foams

For the first time, expandable graphite (EG) and aluminum hydroxide (ATH) was combined to improve the flame retardancy of polyisocyanurate–polyurethane (PIR–PUR) foam. The limited oxygen index increased from 26.5 for the PIR–PUR matrix to an incredible value of 92.8 when 24 phr (parts per 100 of matrix) EG and 60 phr ATH were incorporated into the matrix. Based on morphology observation and thermogravimetric analysis, it was speculated that two factors contributed to the improvement of flame retardancy primarily. First, ATH could effectively induce “villi” like particles, which was useful to form a dense char. The compact char layer could effectively impede the transport of bubbles and heat. Second, ATH and EG accelerated the initial degradation and fluffy char was quickly generated on the surface of the composites. Thus, the degradation of the composite was slowed down and the diffusion of volatile combustible fragments to flame zone was delayed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39936.     

Novel phosphorus‐based flame retardants containing 4‐tert‐butylcalix[4]arene: Preparation and application for the fire safety of epoxy resins

A novel flame retardant (FR) containing phosphorus and 4‐tert‐butylcalix[4]arene was synthesized and characterized. The FR combined with ammonium polyphosphate (APP) was then incorporated into epoxy resins (EPs) at different ratios. The flame retardancy, thermal stability, and smoke‐releasing properties were investigated. The limiting oxygen index was as high as 30.8% when the mass fraction ratio of the FR to APP was 1:2. The improved FR effect have been due to the combined FR effects between the FR and APP. The char residue content at 800 °C under a nitrogen atmosphere increased notably from 8.22% to 17.6% when the FR APP was incorporated into EP; this indicated an improvement in the thermooxidation resistance. From the cone test, we found that both the total heat‐release and peak heat‐release rate of the FR resins were reduced. Compared to the resins containing no FRs, the smoke‐production rate and total smoke‐production results indicate that the FR resins also exhibited good smoke‐suppression properties. Generally, the stable char layer of the FR APP–EP not only effectively prevented the release of combustion gases but also hindered the propagation of oxygen and heat into the interior substrate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45105.     

Effect of graphite on the flame retardancy and thermal conductivity of P‐N flame retarding PA6

In this article, a novel flame‐retardant polyamide 6 (PA6) was prepared by introducing a halogen‐free flame‐retardant (OP1314). Graphite was added as a flame‐retardant synergistic agent, and the flame retardancy was enhanced, especially the melt‐dripping was forbidden and for the formula of PA6/12 wt % OP1314/5 wt % graphite, UL94 V‐0 grade was reached. Meanwhile, the graphite is also an excellent thermal conductive filler and with the addition of 5 wt % graphite in the flame‐retardant PA6 mixtures, the thermal conductivity (λ) rose to 1.2 W/mK which was nearly three times higher than the flame‐retardant PA6. Due to the good flame retardancy and improved thermal conductivity, the material could be suitable for applications in electronic and electrical devices. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46559.     

Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes

Intumescent‐flame‐retarded polypropylene (PP‐IFR) composites were prepared by the incorporation of methyl hydrogen siloxane treated ammonium polyphosphate and dipentaerythritol in a twin‐screw extruder. The effects of zeolite (Z), multiwalled carbon nanotubes (CNTs), and maleic anhydride grafted polypropylene on the flame retardancy, mechanical properties, and thermal stability of PP‐IFR were investigated. The addition of Z and CNT promoted the flame retardancy of PP‐IFR, and the highest limited oxygen index was 35.6%, obtained on PP‐M‐IFR‐2–Z, for which the heat‐release rate, total heat release, and smoke production rate based on cone calorimetry analyses decreased by 45.0, 51.0, and 66.3%, respectively, in comparison with those values of the PP‐IFR composites. Additionally, scanning electron microscopy analyses showed that there was a good interface interaction between the polypropylene matrix and additives. The flexural, tensile, and impact strengths of the PP‐IFR composites were improved significantly with the incorporation of CNT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42875.     

Transparent epoxy resin material with excellent fire retardancy enabled by a P/N/S containing flame retardant

An epoxy resin (EP) with excellent fire retardancy, good transparency, and satisfactory thermal stability has been obtained by introducing a new N/P/S containing flame retardant (HBD) into EP composites. When the phosphorus content was 0.48 wt%, EP/HBD reached V-0 rating with the limiting oxygen index of 33.5%. The cone calorimeter test (CC) indicated that the incorporation of HBD resulted in 1.5 times increase in ignition time, a 50% decrease in the maximum of heat release rates, 40% reduction of total heat release, and 50.7% decrease in total smoke production compared with EP. Besides, the fire-resistant behavior of EP/8% HBD is much better than the EP materials modified by similar P/N/S flame retardants reported in literature. The fire-retardant mechanism of HBD on EP was also analyzed by Raman, scanning electron microscope, Py-GC/MS, and Fourier transform infrared spectroscopy. The results show that HBD plays an important role in the formation of a dense intumescent carbon layer and gas phase quenching.     

Synergistic effects of magnesium oxysulte whisker and multiwalled carbon nanotube on flame retardancy,smoke suppression,and thermal properties of polypropylene

In this work, multiwalled carbon nanotube (MWCNT)-modified magnesium oxysulfate whisker (MOSw) (MOSw-MWCNT) is successfully synthesized via a facial hydrothermal method. MWCNT is bonded on the surface of MOSw via a bidentate bridging mode of the carboxylate ligation without changing their crystal structures. Then MOSw-MWCNT is incorporated into polypropylene (PP) matrix to prepare series of PP/MOSw-MWCNT composites via melt blending. Cone calorimetry test, horizontal and vertical test, and limit oxygen index (LOI) results all show a significant synergistic effect of MOSw and MWCNT on flame-retardant PP. PP/7MOSw-3MWCNT composite exhibits the lowest peak heat release rate, total heat release, peak smoke production rate, total smoke production, and burning speed of 332.3 kW/m², 87.4 MJ/m², 0.0212 m²/s, 47.7 m² and 23.2 mm/min, respectively. The LOI value of PP/7MOSw-3MWCNT composite is increased to 23.1% from 18.0% of neat PP. The scanning electron microscopy and Raman spectra of residue char indicate that the degree of graphitization and compactness of the residue char are increased with the amount of MWCNT. The introduction of MOSw and MWCNT both improves the thermal stability of PP matrix, but the excess MWCNT leads to the decomposition of the unstable residue char since its excellent thermal conductivity.     

Carbon nanoparticles/polyvinyl alcohol composites with enhanced optical,thermal, mechanical,and flame-retardant properties

In this work, polyvinyl alcohol (PVA) is chemically bonded to carbon nanoparticles (CNPs) by a very simple and versatile solution casting method. Five different kinds of CNPs/PVA composite films were prepared; 0.5, 1.0, 1.5, 2.0, and 3.0 wt% CNPs dispersed in PVA. The as-prepared samples were characterized using various characterization techniques. The resulting nanocomposites proved to possess homogeneity and better mechanical, thermal, optical, and flame-retardant properties than pure PVA. Most of the CNPs with average particle size ≤100 nm were homogeneously dispersed in the PVA matrix showing fluorescence in the violet color zone. The crystallinity of the nanocomposites show a decline in the diffraction intensity as compared to pure PVA which results from the dwelling of CNPs inside the gaps of stacked-layer chains of PVA. The mechanical properties of nanocomposites indicated enhancement in toughness, elastic modulus and tensile strength with an increase in CNPs contents. The assessment for flame-retardant properties was carried out through cone calorimetry. The results show a decrease in both total heat release rate (THRR) and peak heat release rate (pHRR) of the resulting nanocomposites as compared to pure PVA. The superior properties of the CNPs/PVA composites stemmed from the good interfacial bonding between the CNPs and PVA matrix.     

Reactive flame retardant with core‐shell structure and its flame retardancy in rigid polyurethane foam

With a shell of poly (methyl methacrylate‐co‐hydroxyl ethyl acrylate) (PMMA‐HA), microencapsulated ammonium polyphosphate (MHAPP) is prepared by in situ polymerization. The core‐shell structure of the reactive flame retardant (FR) is characterized by Fourier transform infrared (FTIR) and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS). The results of water leaching rate and water contact angle measurements show that ammonium polyphosphate (APP) is well coated by a hydrophobic shell. Due to the presence of active groups (–OH) and hydrophobic groups (–CH₃) in shell, MHAPP exhibits better compatibility, flame retardancy, and water resistance compared with neat ammonium polyphosphate (APP) in rigid polyurethane foam (PU). Compression strength of PU/MHAPP with suitable loading is higher than that of PU/APP and PU, the reason is that the active groups in shell can improve the compatibility of MHAPP in PU composite. From thermal stability and residue analysis, it can be seen that the presence of reactive flame retardant shows positive effect on thermal stability of PU composite at high temperature, results also indicate that MHAPP can promote the carbonization formation efficiency of PU composite during combustion process compared with APP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42800.     

Mechanical properties and flame retardancy of PLA composites containing zinc oxide and chain extender

A micro-cross-linked structure had been constructed by the addition of zinc oxide with nanometer-scale particle size (nano ZnO) and chain extender (ADR) into intumescent flame retardant poly (lactic acid) (FRPLA). Flame retardant properties, mechanical properties and thermal stabilities were studied. Limited oxygen index of the FRPLA composite with 1% nano ZnO and 0.8% ADR (FRPLA/0.8ADR/1ZnO) was a maximum (39.4%). T_max and residue at 800°C of FRPLA/0.8ADR/1ZnO was the highest in air. Tensile strength, elongation at break and impact strength of FRPLA/0.8ADR/1ZnO was significantly higher than that which resulted with the addition of either individual filler, indicating that the synergistic effect between nano ZnO and ADR regulated the comprehensive performance of FRPLA. The synergetic effect between nano ZnO and ADR were further illustrated.     

Flame retardancy effects of phosphorus‐containing compounds and cationic photoinitiators on photopolymerized cycloaliphatic epoxy resins

This study presents a promising ultraviolet (UV)‐curable epoxy resin formulation with improved flame‐retardant properties. The formulation is based on the cycloaliphatic epoxide 3,4‐epoxycyclohexylmethyl‐3,4‐epoxycyclohexane carboxylate (ERL4221) and a novel silicon, phosphorous containing flame‐retardant additive. The additive, 1,3,5,7‐tetramethyl‐1,3,5,7‐tetra 2‐(6‐oxido‐6‐H‐dibenzo(c,e) (1,2)oxaphosphorin‐6‐yl) ethylcyclotetrasiloxane (DOPO‐SiD), was synthesized by the addition reaction of 1,3,5,7‐tetramethyl‐1,3,5,7‐tetravinylcyclotetrasiloxane (D₄Vi) with 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO). Formulations containing the cycloaliphatic epoxy resin ERL4221 and the flame‐retardant DOPO‐SiD additive were prepared in various concentrations and crosslinked by UV irradiation. The effects of DOPO‐SiD and photoinitiators, such as the cyclopentadienyl iron complex of carbazole (In‐Fe) and diphenyl‐(4‐(phenylthiol) phenyl) sulfonium hexafluorophosphate (In‐S), on the flame‐retardant properties and thermal stabilities of UV‐cured ERL4221/DOPO‐SiD composites were investigated with limiting oxygen index, UL‐94 vertical test, and thermogravimetric analysis, respectively. The results showed that DOPO‐SiD can increase the thermal stabilities of the ERL4221/DOPO‐SiD. The char yield was improved when DOPO‐SiD and In‐Fe were simultaneously used. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40011.     

A polycarbonate/magnesium oxide nanocomposite with high flame retardancy

A new flame retardant polycarbonate/magnesium oxide (PC/MgO) nanocomposite, with high flame retardancy was developed by melt compounding. The effect of MgO to the flame retardancy, thermal property, and thermal degradation kinetics were investigated. Limited oxygen index (LOI) test revealed that a little amount of MgO (2 wt %) led to significant enhancement (LOI = 36.8) in flame retardancy. Thermogravimetric analysis results demonstrated that the onset temperature of degradation and temperature of maximum degradation rate decreased in both air and N₂ atmosphere. Apparent activation energy was estimated via Flynn–Wall–Ozawa method. Three steps in the thermal degradation kinetics were observed after incorporation of MgO into the matrix and the additive raised activation energies of the composite in the full range except the initial stage. It was interpreted that the flame retardancy of PC was influenced by MgO through the following two aspects: on the one hand, MgO catalyzed the thermal‐oxidative degradation and accelerated a thermal protection/mass loss barrier at burning surface; on the other hand, the filler decreased activation energies in the initial step and improved thermal stability in the final period. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of gas-condensed phase synergistic system of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and polydopamine on flame retardancy of epoxy resin

Polydopamine (PDA) was prepared by using dopamine which has good charring ability. The PDA was used as an environmentally friendly flame retardant and combined with 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO) to improve the flame retardancy of epoxy (EP) resin. The flame retardancy and thermal stability of EP composites were researched by UL-94 vertical burning, limiting oxygen index (LOI), cone calorimetry tests, and thermal gravimetric analyzer. Adding DOPO alone requires 6% to make EP obtain the UL-94 V0. If DOPO and PDA are combined, only 4% is needed to make EP obtain the UL-94 V0, which suggests that there is good synergistic effect between them. Moreover, the peak of heat release rate of EP/DOPO/PDA composites is less than that of EP/DOPO composites. The reactions among EP, DOPO, and PDA reduce the release of combustible gases at the early stage of degradation; at the same time, DOPO volatilize to the gas phase, quench the free radicals, and the combustion can be stopped. In addition, due to the decrease of the amount of PDA/DOPO, the EP composite can get a higher glass transition temperature, but due to the aggregation of PDA in EP, the tensile property of EP composite decreases.     

Flexible and flame resistant poly(lactic acid)/organomontmorillonite nanocomposites

The PLA/OMMT nanocomposites were produced using a melt compounding technique with isopropylated triaryl phosphate ester flame retardant (FR; 10–30 parts per 100 resin). The flammability of the PLA/OMMT composites was evaluated with an Underwriter Laboratory (UL‐94) vertical burning test, and their char morphology was studied using scanning electron microscopy (SEM). The thermal properties of the PLA/OMMT were characterized with a thermogravimetric analyzer (TGA) and a differential scanning calorimeter (DSC). The thermal analyses showed that adding FR reduced the decomposition onset temperature (T_o) of PLA/OMMT. Both PLA/OMMT/FR20 and PLA/OMMT/FR30 showed excellent flame retardant abilities, earning a V‐0 rating during the UL‐94 vertical burning test. A compact, coherent and continuous protective char layer was formed in the PLA/OMMT/FR nanocomposites. Additionally, the DSC results indicated that the flexibility of the PLA/OMMT composites increased after adding FR due to the FR‐induced plasticization. The impact strength of PLA/OMMT was greatly increased by the addition of FR. Flexible PLA nanocomposites with high flame resistance were successfully produced. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41253.